The present invention relates to malodor counteractancy compositions. More particularly, the present invention relates to fragrance compositions containing one or more malodor counteractancy compounds.
Malodors are offensive odors, which are encountered in the air and on many substrates such as fabrics, hard surfaces, skin, and hair. Malodors have either personal or environmental origin. For example sweat, urine, and feces malodors are personal in origin, whereas, kitchen, gasoline, cooking, tobacco smoke, etc. malodors are of environmental origin. While personal malodors are easily deposited on fabric, hair, and skin, environmental malodors also have a propensity to deposit on these substrates. Combinations of personal and environmental malodors make up a composite malodor, which has many oil soluble, water soluble, and solid components that have a vapor pressure at ambient temperatures, which is why humans can detect them.
Amines, thiols, sulfides, short chain aliphatic and olefinic acids, aldehydes, and esters form the largest and most unpleasant chemical groups found in sweat, household, and environmental malodors. These types of malodors typically include indole, skatole, and methanethiol found in toilet and animal odors; piperidine and morpholine found in urine; pyridine and triethyl amine found in kitchen and garbage odors, such as fish; hydrogen sulfide, nicotine, and various pyrroles found in cigarette smoke odors; and short chain fatty acids in axilla malodors.
Several approaches have been used to counteract malodors. These approaches include masking by superimposing the malodor with a pleasant stronger odor, cross-adaptation by blocking of the malodor olfactory receptors, suppression of the malodor by mixing with an ingredient that causes a negative deviation of Raoult""s law, elimination of the malodor by chemical reaction, absorption of the malodor by a porous or cage-like structure, and avoidance of the formation of malodors by such routes as antimicrobials and enzyme inhibitors. All of these approaches are deficient, however, because they provide a perfumer with only limited options for malodor counteractants. Accordingly, there is still a need for additional and improved malodor counteractancy compositions.
It is known that fragrances may be designed to counteract malodors. The fragrance materials, which are most common to mask a malodor are those that contain a carbon-carbon double bond conjugated with one or more carbonyl groups. Aldehydes are the most commonly used materials of this class for malodor counteractancy, the most commonly used for deodorant properties are trimethyl hexanal, other alkyl aldehydes, benzaldehyde, and vanillin. For example, European Patent Application 0404470 discloses the use of fragrance materials with good malodor reduction efficacy, and European Patent Application 0545556 discloses mixtures of fragrance materials that mask malodors. The use of fragrance materials alone, however, may limit the types of fragrances a perfumer can create.
Other materials have also been shown to have malodor counteractancy (MOC) properties. Schleppnik, U.S. Pat. No. 4,622,221 (xe2x80x9cSchleppnik ""221xe2x80x9d) discloses the use of cyclohexyl alcohols and ester derivatives in room fresheners. Kulka, U.S. Pat. No. 3,074,891 discloses esters of alpha-, beta-unsaturated monocarboxylic acids as malodor counteractants. Kulka, U.S. Pat. No. 3,077,457 discloses fumaric acid esters as malodor counteractants. Schleppnik, U.S. Pat. No. 4,187,251 discloses alkyl cyclohexyl alkyl ketones as malodor counteractants. Schleppnik, U.S. Pat. No. 4,310,512 discloses the use of derivatives of acetic and propionic acids, and Schleppnik et al., U.S. Pat. No. 4,009,253 discloses the use of 4-cyclohexyl-4-methyl-2-pentanone as a malodor counteractant. These materials, however, are not capable of neutralizing all types of functional groups contained in malodor molecules. All of the U.S. patents discussed above are hereby incorporated by reference as if recited in full herein.
Unsaturated non-perfumery chemical compounds have also been shown to act as effective deodorants on the basis that many reactive odor-causing molecules may be eliminated by addition across the double bond. Unfortunately, many of the unsaturated compounds themselves have very unpleasant and offensive odors.
While all of the approaches set forth above are designed to mitigate malodors, none of them adequately eliminates the malodor. Accordingly, a need exists for compounds that counteract malodors alone, or in combination with other malodor counteractants. Ideally, the compounds should have little or neutral odors so that they may also be used in products that contain fragrance.
Accordingly, one embodiment of the invention is a composition containing a Class A compound of the formula: 
wherein
R1 is an hydrogen, an alkyl, an alkoxy, a substituted or unsubstituted aryl; and
R2 is an alkyl having more than 6 carbon atoms, an aryl or a substituted aryl, and the Class A compound exhibits a malodor counteractancy (MOC) effect.
Another embodiment of the invention is a process for dispersing a malodor counteractancy (MOC) composition into a space. This process includes:
(a) incorporating into a consumer product a MOC composition containing a Class A compound of the formula: 
xe2x80x83wherein
R1 is an hydrogen, an alkyl, an alkoxy, a substituted or unsubstituted aryl; and
R1 is an alkyl having more than 6 carbon atoms, an aryl or a substituted aryl; and
(b) dispersing an effective amount of the consumer product to achieve a MOC effect in the space.
A further embodiment of the invention is a process for imparting a MOC effect to a substrate. This process includes:
(a) contacting a substrate with a consumer product containing a Class A compound of the formula: 
xe2x80x83wherein
R1 is an hydrogen, an alkyl, an alkoxy, a substituted or unsubstituted aryl; and
R2 is an alkyl having more than 6 carbon atoms, an aryl or a substituted aryl, which Class A compound has a MOC effect.
Another embodiment of the invention is a fragrance composition containing:
(a) a Class A compound having a malodor counteractancy (MOC) effect of the formula: 
xe2x80x83wherein
R1 is an hydrogen, an alkyl, an alkoxy, a substituted or unsubstituted aryl; and
R2 is an alkyl having more than 6 carbon atoms, an aryl or a substituted; and
(b) a fragrance.
We have surprisingly found that certain aromatic unsaturated carboxylic esters wherein the unsaturation is conjugated to both the aromatic ring and the carbonyl group portion of the carboxylic ester counteract malodors. This malodor counteractancy effect is additive to that achieved by some classes of known malodor counteractancy ingredients and, therefore, provides an additional advantage to e.g., perfumers who require low odor intensity or neutral odor malodor counteractancy compounds. More surprisingly, these compounds may act synergistically with specific known MOC compounds.
As used herein, malodor counteractancy (xe2x80x9cMOCxe2x80x9d) means the reduction of the perception of the offensiveness of a malodor or malodors to the human sense of smell. In the present invention, MOC is evaluated as set forth in the Examples. As used herein, a MOC effect is said to be xe2x80x9cadditivexe2x80x9d when the malodor counteractancy effect of a MOC composition is equal to the sum of the malodor counteractancy effects of each MOC compound in the composition alone. An effect is said to be xe2x80x9csynergisticxe2x80x9d when the malodor counteractancy effect of a MOC composition is greater than the sum of the malodor counteractancy effects exhibited by each MOC compound in the composition alone.
The present invention provides a composition containing a compound or mixture of compounds having low odor intensity or neutral odor that counteracts malodors.
In the present invention, compounds having an aromatic unsaturated carboxylic ester, wherein the unsaturation is conjugated to both the aromatic ring and the carbonyl group of the carboxylic ester have been found to counteract malodors. These molecules have the structure shown below, and are designated herein as Class A compounds: 
wherein
R1 is an hydrogen, an alkyl, an alkoxy, an aryl, or a substituted aryl, preferably R1 is H, a C1 to C8 alkyl, a C1 to C8 alkoxy, or an aryl; and
R2 is an alkyl having greater than 6 carbon atoms, an aryl, or a substituted aryl group, preferably, R2 is a C6 to C12 alkyl or an aryl.
Preferably, the Class A compounds have a low odor intensity. As set forth in more detail in Example 5, in the present invention, compounds with low odor value are preferred because they are easier to incorporate into a fragrance composition. Thus, as used herein, a compound with a low odor intensity is defined as one having an Odor Value of less than 1000, preferably an Odor Value of less than 500. In the present invention, xe2x80x9cOdor Valuexe2x80x9d is the quantity of compound in the headspace in nanograms per liter divided by its perception threshold as in nanograms per liter. Odor Value is determined by the methods disclosed by Nuener-Jehle and Etzweiler (Neuner-Jehle N. and Etzweiler F., Perfumes Art Science and Technology, Chapter 6, p 153, Elsevier Science Publishers LTD, England.)
In the present invention, the Class A compounds may be combined with certain Class B MOC compounds to provide an additive MOC effect. As used herein, the Class B MOC compounds that are combinable with the Class A compounds of the present invention have an Odor Value of less than 1000, preferably less than 500. Class B compounds that are useful in the present invention (a) have a MOC effect of less than 1000, preferably less than 500 and (b) when combined with a Class A compound of the present invention exhibit at least an additive, preferably a synergistic MOC effect as determined using the methods set forth in one of the Examples below. In the present invention, when combinations of Class A and Class B compounds are used, the composition should also have an Odor Value of less than 1000, preferably less than 500.
Thus, in the present invention, the Class B MOC compounds include, for example, aliphatic alpha unsaturated dicarboxylic esters wherein the double bonds are bracketed between carbonyl groups, cycloalkyl tertiary alcohols, esters of alpha-, beta-, unsaturated monocarboxylic acids, and 4-cyclohexyl-4-methyl-2-pentanone. Preferably, the Class B compounds are geranyl crotonate, dihexyl fumerate, cyclohexylethylisobutyrate, and cyclohexylethylhexanoate. Moreover, mixtures of Class B compounds may also be used, such as for example a mixture of dihexyl fumerate 
Optionally, the MOC compositions as defined above (i.e., compositions containing a novel Class A compound as set forth above and compositions containing a mixture of Class A and B MOC compounds) may be used in combination with a fragrance, preferably with a fragrance that has a MOC effect. For purposes of the present invention, a fragrance that has a MOC effect is a mixture of fragrance ingredients, which in combination reduce the perception of a malodor as measured by one of the methods set forth in the examples. In the present invention, the fragrance ingredients may be selected from alcohols, aldehydes, ketones, esters, acetals, oximes, nitriles, ethers, essential oils, and mixtures thereof.
The amount of a Class A MOC compound alone or a mixture of Class A and Class B compounds required for effective malodor counteractancy depends upon the type of product into which such a compound or mixture of compounds is incorporated. For example, if no fragrance is present in the product, then a minimum amount of a Class A MOC compound is required, such as 0.1% (wt), preferably 0.2% (wt). In a product containing a fragrance, the Class A compound according to the present invention is required to be present at a minimum of 0.01% (wt), preferably 0.025% (wt). These same ranges also apply to fragrance-less compositions containing mixtures of MOC compounds.
When a fragrance is used in a MOC composition according to the present invention, more of the Class A and/or B MOC compound(s) will typically be required. For example, when a fragrance is used, the MOC compounds are present in the composition at greater than 1% (wt) of the fragrance, preferably at greater than 5% (wt) of the fragrance.
In compositions containing a mixture of Class A and B compounds, the ratio of Class A to Class B compounds is 1:99 to 70:30, preferably 5:95 to 70:30.
Antimicrobial agents may be incorporated into the present compositions. Such antimicrobial agents include, for example, metal salts such as zinc citrate, zinc oxide, zinc pyrethiones, and octopirox; organic acids, such as sorbic acid, benzoic acid, and their salts; parabens, such as methyl paraben, propyl paraben, butyl paraben, ethyl paraben, isopropyl paraben, isobutyl paraben, benzyl paraben, and their salts; alcohols, such as benzyl alcohol, phenyl ethyl alcohol; boric acid; 2,4,4xe2x80x2-trichloro-2-hydroxy-diphenyl ether; phenolic compounds, such as phenol, 2-methyl phenol, 4-ethyl phenol; essential oils such as rosemary, thyme, lavender, eugenol, geranium, tea tree, clove, lemon grass, peppermint, or their active components such as anethole, thymol, eucalyptol, farnesol, menthol, limonene, methyl salicylate, salicylic acid, terpineol, nerolidol, geraniol, and mixtures thereof.
In the present invention, malodor adsorbers may also be incorporated into the present MOC compositions. As used herein, xe2x80x9cmalodor adsorbersxe2x80x9d are any material that adsorbs malodor in sufficient quantities to provide a reduction in malodor perception, and which do not reduce the MOC effectiveness of the compositions of the present invention. Such malodor absorbers include, for example, inorganic absorbents, including molecular sieves, such as zeolites, silicas, aluminosilcates, and cyclodextrins; and organic absorbents, such as for example, activated charcoal, dried citrus pulp, cherry pit extract, corncob, and mixtures thereof.
The MOC compositions of the present invention may be incorporated into various products, e.g., consumer products, such as for example the products set forth in more detail below.
The present invention also includes a process for dispersing the MOC compositions of the present invention into a space. This process includes incorporating into a composition, such as for example, a consumer product, a MOC composition containing a Class A compound as defined above and dispersing an effective amount of the consumer product to achieve a MOC effect in the space. In addition, the MOC composition may contain a mixture of Class A and Class B compounds as defined above.
As used herein, an xe2x80x9ceffective amountxe2x80x9d of the composition, e.g., consumer product, will vary depending upon the intended use, the composition used, the ambient conditions, and other well known variables. Using the examples provided below, one skilled in the art may judge the appropriate amounts of the MOC compositions to be used in order to dispense an effective amount of, e.g. the consumer product, into the space.
As used herein, xe2x80x9cconsumer productsxe2x80x9d include, for example, sprays, candles, gels, plug-in electrical devices and battery-operated devices for introducing compositions into spaces, and liquid wicking systems. In the present invention, the sprays may be aqueous or non-aqueous. The candles and gels of the present invention may be opaque, translucent, or transparent, and may contain optional ingredients to enhance their appearance. The plug-in and battery-operated devices may include devices that vaporize the fragrance by heat, evaporation, or nebulization.
In this process, the dispersing step may be achieved by, for example spraying, atomizing, and volatilization. Typically, the MOC composition is then dispersed into, for example, rooms, closets, chests, and draws.
The present invention also provides a process for imparting a MOC effect to a substrate. This process includes contacting a substrate with a composition, such as a consumer product, containing a Class A compound that has a MOC effect. In addition, Class B compounds that have a MOC effect as defined above may also be combined with the Class A compounds. In this process, the substrate may be either hair or skin. And, the consumer product used in this process may be any one of the products defined below.
The products of the present invention that are to provide MOC when applied to the skin may include, for example, talcum powder, deodorants and antiperspirants in the form of sprays, soft solids, and solids, lotions, and oils.
In the present invention, the Class A and Class B compounds may be incorporated into products that are used to clean the skin, and to provide a MOC to the skin. Such products include, for example, soap, syndet, and combination soap and syndet personal wash bars, personal wash liquids, and personal wipes.
As noted above, the Class A and Class B compounds may be incorporated into products, and used in processes, that are to provide a MOC effect to the hair. Such products, include for example, shampoos, conditioners, styling sprays, mousses, gels, hair wipes, hair sprays, and hair pomades.
The products and processes of this invention that are to provide a MOC effect by treating a substrate may include or utilize, for example, fabric washing liquids and powders, fabric conditioners, wipes, dishwashing liquids and powders, hard surface cleaning liquids and powders, and aqueous and non-aqueous sprays.
The present invention also provides fragrance compositions containing a Class A compound as defined above having a MOC effect in combination with a fragrance. In this composition, the fragrance may be any art recognized fragrance composition, preferably one also having a MOC effect. The fragrance composition may further include a Class B compound as defined above having a MOC effect, wherein the MOC effect of the Class A and Class B compounds is additive, preferably synergistic.
The fragrance compositions may include any of the Class A compounds set forth in Table 1 below. Preferably, the Class A compound is OMC (octyl methoxy cinnamate). If a mixture of Class A and Class B compounds is desired, preferably the Class B compounds will be selected from aliphatic alpha unsaturated dicarboxylic esters wherein the double bonds are bracketed between carbonyl groups, cycloalkyl tertiary alcohols, esters of alpha-, beta-, unsaturated monocarboxylic acids, and 4-cyclohexyl-4-methyl-2-pentanone. Preferably, the Class B compound is selected from dihexyl fumarate, cyclohexylethylisobutyrate, and cyclohexylethylhexanoate. More preferably, the Class B compound is dihexyl fumerate. Thus, when a mixture of Class A and Class B compounds is desired, it is preferred that the Class A compound be OMC and that the Class B compound be dihexyl fumerate.
The following examples are provided to further illustrate the compounds, compositions, and processes in accordance with the invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way. In these examples, all % are % (wt), unless otherwise noted.